Diepoxides of ether acetals of 1, 1-bis-(hydroxymethyl)-cyclohexene



3,072,678 Patented Jan. 8, 1963 3,072,678 DIEPOXEDES F EITHER ACETALS 0F LLBIS- (HYDROXYMETHYD-CYCLQHEXENE Daniel Porret, Basel, Willy Fisch, Binningen, Hans Batzer,

A'rlesheim, and (Mo Ernst, Pfeflingen, Switzerland, as-

signors to Cilia Limited, Basel, Switzerland, a company of Switzerland No Drawing. Filed Sept. 8, 1960,8er. No. 54,581 Claims priority, application Switzerland ept. 10, 1959 4 Claims. ((1l.'260--34il.7)

The present invention provides new acetals which contain at least two epoxide groups and correspond to the CPI-(EH-Cffk-O-Z] formula m X1 X2 (1) in which X and X each represent a hydrogen atom or a methyl group; Z represents an organic radical containing at least one epoxide group; n is a small whole number, and Y represents the radical of a polyhydric alcohol with 2n free valences and, when 11:1, the radical Y must contain at least one epoxide group.

The new acetals are obtained by the present process when,

(A) An acetal, which contains at least one epoxidizable group, of the formula 0 Y I: CHCHOHO-Z:

O/ 1 11 2 12 n (II) in which X and n have the same meanings as in Formula I; Z represents an organic radical which contains at least one epoxide group or an epoxidizable group; and Y represents the radical of a polyhydric alcohol with 2n free valences and, when n=1, the radical Y must contain at least one epoxide group or epoxidizable groupis treated with an epoxidizing agent; or

(B) n mols of a compound of the formula Z-OH are added on to one mol of an unsaturatedacetal of the formula Y on o=on I; I i] -o X1-Xg III) in which formulae X X 11, Z and Y have the same meanings as in Formula I.

The term radical containing an epoxidizable'group designates above all radicals containing epoxidizable car- 'bon-to-carbon'double bonds, such as an allyl, butenyl or tetrahydrobenzyl radical. When acted upon, for example, with an organic per-acid, such carbon-to-carbon double bonds can be epoxidized to yield the 1:2-epoxide group.

The term radical containing an epoxidizable group further designates radicals containing a halohydrin groupmost readily by acetalizing methacrolein or preferably crotonic aldehyde or acrolein with the dialcohol orpolyalcohol.

In this connection two cases have to be distinguished:

(l) The polyalcohol used contains as such at least one unsaturated group which can be directly epoxidized in'a second stage or after an additive reaction with an alco- 1101 of the formula ZOH or Z'-OH can be converted into an epoxy compound. In this case there may be used polyalcohols containing at least two hydroxyl groups.

(2) The polyalcohol is free from double bonds, in which case it must contain at least four hydroxyl groups.

In case (1) there may be mentioned as unsaturated polyalcohols, for example:

Butene-(2)-diol-l:4, glycerol monoallyl ether, butanetriol-(l:2:4)-monoallyl ether and the like, furthermore above all dialcohols of the formula a a Rs C CHzOH in which R to R each represent monovalent substituents, such as halogen atoms, alkoxy groups or aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radicals, more especially alkyl radicals'with l to 4 carbon atoms, or hydrogen atoms, wherein R and R together may also represent an alkylene radical, such as a methylene group. As examples of such dialcohols'IV there may be mentioned:

1: l-bis- [hydroxymethyl] -cyclohexene- 3 1 l-bishydroxymethyl] -6-methylcyclohexene- 3 1 l-bis- Lnydroxymethyl] -2 4 o-trimethylcyclohexene- 1 l-bis- [hydroxymethyl] -2 5-endomethylene-cyclohexene- 3 and 1 l-bis- [hydroxymethyl] -4--chlorocyclohexene- (3 In case (2) there may be mentioned as polyalcohols containing at least four hydroxyl groups the following:

Erythritol, xylitol, arabitol, sorbitol, mannitoL-dulcitol, talitol, iditol, adonitol and pentaerythritol, heptitols, 212:6:6-tetramethylolcyclohexanol-(1); also polyalcohols that additionally contain other functional groups, for example sugars, such as glucose, gal'actose, mannose, fructose, sucrose and the like; sugar acids such as glucoronic acid, galacturonic acid, mucic acid and the like. Finally, there may be used as polyalcohol a polymer containing free hydroxyl groups, such as a polysaccharide and more especially polyvinylalcohol or partially hydrolysed polyvinyl acetate. The acetalization may follow the usual pattern and consists, for example, in heating an aldehyde of the formula H (V) together with the diol or polyol in the presence of an acid catalyst, such, for example, as hydrochloric or paratoluenesulfonic acid.

This procedure yields at first an unsaturated acetal of the formula Y /CHC=CH -0 1 X2 11 (VI) To obtain the acet'als of the Formula II an alcohol of the formula Z-OH is added in a second stage on to the double bond of the unsaturated acetal IV. As a rule, the alcohol Z'OH contains "an *epoxidizable group. There may be mentioned chlorohydrin, for example amethylglycerol-u-monochlorohydrin, fi-methylglycerol-umonochlorohydrin, glycerol-B-monochlorohydrin, glycerol-a-bromohydrin and more especially gIYCBIGI-oc-IHOHO- chlorohydrin as well as mixtures of such monochlorohydrins, for example the commercial mixture of glycerol fl-monochlorohydrin and glycerol-a-monochlorohydrin; furthermore unsaturated alcohols such as allyl'alcohol, crotyl alcohol, octadecenyl alcohol, A -cyclohexanol-l, dehydronorborneol, dihydrodicyclopentadienol-8 and more especially those of the formula (VII) in which R to R each represent monovalent substituents such as halogen atoms, alkoxy groups or aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radicals, more especially lower alkyl groups containing 1 to 4 carbon atoms, or hydrogen atoms, in which formula R and R together may also constitute an alkylene radical such as a methylene group. As examples of such alcohols VII there may be mentioned: A -tetrahydrobenzyl alcohol, 6- methyl-A -tetrahydrobenzyl alcohol, 2:4: 6-trimethyl-A tetrahydrobenzyl alcohol, l:S-endomethylene-h -tetrahydrobenzyl alcohol and 4-chloro-A -tetrahydrobenzy1 alcohol.

When the unsaturated acetal VI is derived from an unsaturated polyol (n in Formula VI is preferably=l), x mols (x=not a whole number) of such an acetal can be added on to 1 mol of a polyhydroxy compound containing x hydroxyl groups.

As such polyhydroxy compounds there are suitable above all aliphatic or cycloaliphatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols, propanediol, polypropyleneglycols, butanediol, pentanediol, hexanediol; glycerol, 1:1:1-trimethylolpropane, sorbitol, mannitol, pentaerythritol; quinitol, resorcitol.

This procedure gives rise to epoxidizable acetals, for example of the type (G=radical of the diol) that is to say that the radical Z in Formula II is a radical of the formula As relevant examples may be mentioned the adducts of 2 mols of the acetal of acrolein and 1:1-bis-(hydroxymethyl)-cyclohexene-3 with 1 mol of a glycol or polyglycol such as ethylene glycol.

Instead of a diol or glycol there may be used water for the additive reaction of 2 mols of an unsaturated acetal VI derived from an unsaturated diol, whereby a simple ether of the formula is obtained, that is to say that the radical Z in the Formula II is in this case a radical of the formula Furthermore, 1 to (x-l) mols of an unsaturated acetal VI derived from an unsaturated diol may be added onto 1 mol of a polyhydroxy compound containing x hydroxyl groups. The free hydroxyl group(s) of the resulting adduct can then be further reacted with compounds containing in addition to epoxidizable groups such groups as can be condensed with hydroxyl groups, for example carboxyl or hydroxyl groups, halogen atoms or the like.

Thus, for example, in a first stage 1 mol of the acetal of acrolein and 1:l-bis-[hydroxymethyl]-cyclohexene-3 can be added on to 1 mol of a glycol or polyglycol, and in a second stage the resulting adduct is etherified, for example, with 1 mol of epichlorohydrin or A -tetrahydro benzyl alcohol or dihydrodicyclopentadienol or esterified with 1 mol of A -tetrahydrobenzoic acid.

When the radical of the polyol contains additionally at least one epoxidizable group, acetals of the Formula II are also obtained when in a second stage an alcohol of the formula Z'0H or ZOH which as such contains an epoxide group, is added on. As examples of such alcohols may be mentioned glycidol or more especially epoxidized hydroaromatic alcohols of the formula such as 3:4-epoxy-hexahydrobenzyl alcohol.

By subjecting such an alcohol ZOH containing an epoxide group to an additive reaction with an acetal III there are obtained by the variant B of the present process directly the new epoxides of the Formula 1. However, in this case the radical of the polyol no longer contains any epoxidizable groups; it contains either an epoxide group or is free from epoxide groups. The former is the case when the radical is that of a diol, the latter in general when the radical is that of a polyol containing at least four hydroxyl groups.

The additive combination of the alcohol Z'-OH or ZOH with the carbon-to-carbon double bond of the aldehyde radical is advantageously carried out in the known manner, in the presence of a basic catalyst, such as sodium hydroxide, or more especially of an acid catalyst or a Lewis acid, such as sulfuric acid or boron trifiuoride.

According to the variant A of the present process the acetal II, which still contains at least one epoxidizable group such as an epoxidizable carbon-to-carbon double bond or a halohydrin group, is treated with an epoxidizing agent.

The epoxidation of the carbon-to-carbon double bond yielding the compound of the present invention is carried out by a conventional method, preferably with the aid of an organic per-acid, such as peracetic, perbenzoic, peradipic, monoperphthalic acid or the like. Another suitable epoxidizing agent is hypochlorous acid; when this substance is used HOCl is added on to the double bond in a first stage, whereupon in a second stage, by treatment with a hydrogen chloride donor, for example a strong alkali, the epoxide group is formed.

In correspondence with what has been said above with respect to the meaning of the term radical containing an epoxidizable group, the treatment according to the invention with the epoxidizing agent includes also the treatment with an agent capable of splitting off hydrogen halide (such as potassium hydroxide or sodium hydroxide) of halohydrin groups, for example the glycerol:

monochlorohydrin group, with formation of the corresponding 1:2-epoxide group or of a glycidyl group.

When the acetal 11 contains epoxidizable carbon-to-carbon double bonds as well as halohydrin groups, the epoxidation is performed in two stages: advantageously, the carbon-to-carbon double bonds are first epoxidized and the halohydrin groups are then converted into epoxide groups.

The epoxidation may lead, in addition to the diepoxides or polyepoxides respectively, to wholly or only partially hydrolysed epoxides stemming from side reactions, that is to say compounds in which the epoxide groups of the polyepoxide I have been wholly or partially hydrolysed to hydroxyl groups.

The present invention is based on the observation that in general the presence of such by-products has a favourable effect on the technical properties of the cured polyepoxides; accordingly it is in general of advantage not to isolate the pure polyepoXide from the reaction mixture.

The epoxidized acetals of the present invention may also contain, of course, other functional groups, depending on the polyols and on the alcohols Z-OH from which they are derived. More especially, there may be present in addition to the acetalized hydroxyl groups of the polyol, free hydroxyl groups so that certain properties, such as the adhesivity or hydrophilicity or the curing speed of the epoxide compounds of the invention can be modified extensively.

Particularly advantageous properties are found in the diepoxides of the general formula in which X stands for a methyl group or for a hydrogen atom, and R to R and R to R each stand for monovalent substituents such as halogen atoms or aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radicals, more especially for alkyl radicals with 1 to 4 carbon atoms, or for hydrogen atoms, and in which R and R together or R and R together may also form an alkylene radical such as a methylene group.

Most readily available are the diepoxide compounds of the formula in which X represents a hydrogen atom or a methyl group, and R and R each represent a hydrogen atom or a lower alkyl radical.

The epoxides defined above are bright, viscid or fusible resins which can be converted with suitable curing agents such, for example, as dicarboxylic anhydrides, into clear, bright, cured products having excellent technical properties, more especially an outstandingly high thermal stability according to Martens.

Similarly valuable technical properties'are also found in the-diepoxide compounds of the formulae in which the radicals X R and R to R have the same meanings as in Formulae XI and XII.

Further distinguished by their advantageous properties are the polyepoxide compounds of the general formula in which X and X each stand for hydrogen atoms or methyl groups and the radicals R to R and R to R have the same meanings as in Formula XI and R has the same meaning as R and A represents a tetravalent aliphatic radical which contains at least four carbon atoms, none of which has more than a single free valence; the aliphatic radical A may be unsubstituted or substituted, for example, by hydroxyl, ether, sulfide, carboxyl, carboxylic acid ester groups, keto, aldehyde, acetal groups or the like.

In an important special case the radical A may be substituted by more than 2, for example, 3, 4 or more, acetal groupings of the formula Also in this case, there are most readily accessible the diepoxide compounds of the formula in which X and X each stand for hydrogen atoms or methyl groups, R and R for hydrogen atoms or lower alkyl groups, and A for a tetravalent saturated aliphatic hydrocarbon radical which may be substituted by at most two hydroxyl groups and which contains 4, or 6 carbon atoms, none of which contains more than a single free carbon radical which may be interrupted by oxygen atoms; and 2:1 or 2.

The most advantageous manner of preparing these preferred diepoxide compounds of the Formulae XI, XII, XV or XVIII is to react an epoxidizing agent on a hydroaromatic acetal of any one of the formulae valence, and furthermore no hydroxyl groups may be R2 R1 R1 R2 bound to carbon atoms having such a free valence. O CH2 The epoxrdes consntute bright, fusible resins which can be converted with suitable curing agents, for example d1- I c carboxylic anhydrides, into clear, bright, cured products I 2 having excellent technical properties. RP (PR5 RBLC Furthermore, there may be mentioned in this connec- C\ R1 R7 /C tron triepoxide compounds of the formula R, R, (XX) R R,

/o\z o /0\ CH: CH GHCHz-O-OHCHz-Cfi CH-OHrCH-OCHz-C CH I l o\ X; OA-O X1 /0 g HR 0\ 0 R'-OE\I CH CH2 v 0% CH: +112 CH-X1" 5 (EH; JH-R" CE CH2 l/ (XVII) 0 in which X X and X each stand for hydrogen atoms on or methyl groups, R, R and R for hydrogen atoms or g I I lower alkyl radicals, and A represents a hexavalent sat- CHfiO urated aliphatic hydrocarbon radical which contains 6 CH2 0-0111 0 carbon atoms, none of which has more than a single free CH l fl valence. 40 I f The properties of these last-mentioned epoxides resem- H l ble those of the epoxides of the Formula XVI. Rs'-C R4' Products that likewise have a considerable practical 4 importance are the diepoxide compounds of the general XXI 4 formulae 5 R:\ /R1 Ri Rn /o\ /CH2-O\ /OCH\; 0 R370 c\ /CHCIIz-(EH-OEGO3--$H-CHy-C 0 C-Ra o GHQ-o X, HXU 0oi o B|C\ /CRg Rg'- CR4' R7 R R6 (XVIII) R, R and CH1 CEZO O--CH: CH /c o\ CH-CHz--(IJHOEGOJ Cl)HCHzC\ C CI\I o 0112-0 X D X, 0-06 I l 0 CH CH-R B UE /C CH1 (XIX) CH: in which the radicals X X R to R and R to R have the same meanings as in the Formulae XV and r XVI; G represents an aliphatic or cycloaliphatic hydro- K 2 t 2* i 0 I o CCH;-O---CH--GH1CH A CHCHzCHOCH;-C C--Ra l l Tn X1 0 0 X1 0-H! Rr-o -ru a o R4 A RI a Ra R4,

(XXII) in which X X R to R R to R A, G and p have 10 the same meanings as in Formulae XI, XIII, XV, XVIII. The acetals of the Formulae XX and XXI are obtained in the simplest manner as follows:

Acrolein or crotonic aldehyde is acetalized with a diol IV, whereby an acetal of the formula 1 is obtained which is then subjected to an additive reaction with a hydroaro-matic alcohol of the Formula VII or with dihydrodicyclopentadienol-8, whereby the acetal XXIV is obtained.

The acetals of the Formula XXII are easiest to prepare in the following manner:

Acrolein or crotonic aldehyde is acetalized with a polyol which contains at least 4 hydroxyl groups, whereby a spirocyclic acetal of the formula 0 0 35 CH=CHG A \CHOH=CH in o 0 in (XXV) is obtained, of which 1 mol is added on to 2 mols of a hydroaromatic alcohol of the Formula VII.

In a similar manner there can be prepared the derivatives of dihydrodicyclopentadienol by adding on to 2 mols thereof 1 mol of acetal XXV.

The acetals of the Formula XXIII are easiest to prepare by an additive reaction of 2 mols of an acetal XXIV with 1 mol of water (p -1) or 1 mol of a diol of the formula HOGOH (12:2).

Instead of first preparing a hydroaromatic acetal of the Formula XX or XXII and treating it with an epoxidizing agent, the diepoxide compounds of the Formula XI or XV are also obtained by adding an epoxidized hydroaromatic alcohol X on to an acetal XXIV or XXV.

The epoxidized acetals of the present invention react with the conventional curing agents for epoxide compounds; with the aid of such curing agents they can be cross-linked or cured in the same manner as other polyfunctional epoxide compounds or epoxy resins. Suitable relevant curing agents are basic or more especially acidic compounds.

Good results have been achieved with amines or amides, such as aliphatic and aromatic primary, secondary and tertiary amines, for example monobutylamine, dibutylamine, tributylamine, para-phenylenediamine, bis- [para-aminophenyl] -methane, ethylenediamine, N:N diethylethylenediamine, N:N-dimethylpropylenediamine, diethylenetriamine, tetra- [hydroxyethyl] -diethylenetriamine, triethylenetetramine, tetraethylenepentamine, trimethylamine, diethylamine, triethanolamine, Mannichs bases, piperidine, piperazine, guanidine and guanidine derivatives such as phenyldiguanidine, diphenylguanidine, dicyandiamide, aniline-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, polymers of aminostyrenes, polyamides, for example those of aliphatic polyamines and dimerized or trimerized unsaturated fatty acids, isocyanates, isothiocyanates; polyhydric phenols, 75

for example resorcinol, hydroquinone, bis-[4-hydroxyphenyl]-dirnetl1ylmethane, quinone, phenolaldehyde res ins, oil-modified phenolaldehyde resins, reaction products of aluminum alcoholates or phenolates with compounds of tautomeric reaction of the type of the acetoacetic ester, Friedel-Crafts catalysts, for example aluminum chloride, antimony pentachloride, tin tetrachloride, zinc chloride, boron trifiuoride and complexes thereof with organic compounds, metal fiuoborates, boroxines, or phosphoric acid. Preferably used curing agents are poly basic carboxylic acids and anhydrides thereof, for example phthalic anhydride, methylendomethylene-tetrahydrophthalic anhydride, dodecenyl-succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexachloroendomethylene-tetrahydrophthalic anhydride or endomethylene-tetrahydrophthalic anhydride or mixtures thereof; maleic or succinic anhydride; if desired, accelerators may be used additionally, such as tertiary amines or strong Lewis bases, such, for example, as alkali metal alcoholates, and advantageously polyhydroxy compounds such as hexanetriol, or glycerol.

It has been observed that in curing the epoxy resins of the invention with carboxylic anhydrides it is of advantage to use for every gram equivalent of epoxide groups only about 0.3 to 0.9 gram equivalent of anhydride groups. When a basic accelerator is used, such as an alkali metal alcoholate or an alkali metal salt of a carboxylic acid, up to 1.0 gram equivalent of anhydride groups may be used.

The term curing" as used in this connection refers to the conversion of the epoxide compounds described above into insoluble and infusible resins.

Accordingly, the present invention also provides curable mixtures containing the epoxidized acetals according to the invention as well as curing agents for epoxy resins, preferably an anhydride of a dicarboxylic or polycarboxylic acid.

The curable mixtures of the present invention further contain with advantage a certain share of otherwise suitable acetals whose epoxide groups, however, are wholly or partially hydrolysed to hydroxyl groups and/or other polyhydroxy compounds displaying a cross-linking action, such as hexanetriol. It will be readily understood that the curable epoxide compounds may also contain other epoxides such, for example, as monoor polyglycidyl ethers of monoor polyalcohols such as butanol, 1:4- butanediol or glycerol, or of monoor polyphenols such as resorcinol, bis-[4-hydroxyphenyl]-dimethylmethane or condensation products of aldehydes with phenol (novolaks); furthermore polyglycidyl esters of polycarboxylic acids such as phthalic acid, and also aminopolyepoxides such as are obtained, for example, by dehydrohalogenating a reaction product of an epihalohydrin with a primary or secondary amine, such as n-butylamine, aniline or 4 4-di- (monomethylamino) -d iphenylmethane.

The curable epoxide compounds or mixtures thereof with curing agents may also be treated before the curing at any desired phase with a filler, plasticizer, coloring matter or the like. Suitable extenders and fillers are, for example, asphalt, bitumen, glass fibers, mica, quartz meal, cellulose, kaolin, finely dispersed silicic acid (Aerosil) or metal powders.

The mixtures of the new epoxide compounds and curing agents can be used with or without fillers, if desired in the form of solutions or emulsions, as textile assistants, laminating resins, paints, lacquers, dipping resins, casting resins, coating compositions, pore-fillers, putties, adhesives, moulding compositions or the like, as well as for the manufacture of such products. The new resins are particularly valuable as insulating compounds for the electrical industry.

In the following examples parts and percentages are by weight, the relationship between parts by weight and parts by volume being the same as that between the kilogram and the liter.

EXAMPLE 1 (a) Aeetal of Acrolein and 1:1-Bis-[Hydroxymethyl1- Cyclohexene-3 A mixture of 118 parts of acrolcin, 286 parts of 1:1- bis-[hydroxymethyl]-cyclohexene-3 and 3 parts by volume of sulfuric acid of 50% strength is heated for 20 minutes at 50 C. When all has passed into solution, 700 parts by volume of benzene and 2 parts of para-toluenesulfonic acid are added and the whole is boiled for 40 minutes in a circulation distillation apparatus until 40 parts of Water have distilled over azeotropically. The solution is treated with 4 parts of anhydrous sodium carbonate, filtered and evaporated. The benzene is distilled ed at 54-61 C. under a pressure of 0.2 mm. Hg, and 319 parts of acetal (3-vinyl 2:4 dioxspiro(5 :5) undecene-9) pass over which corresponds to a yield of 87% of the theoretical. There remain 40 parts of an unidentified residue.

(b) Additive Reaction With A -Tetrahydrobenzyl Alcohol A mixture of 225 parts of the acetal described above (3-vinyl-2:4-dioxospiro(5:5)-undecene-9), 140 parts of A -tetrahydrobenzyl alcohol, 0.5 part by volume of concentrated sulfuric acid and 0.5 part by volume of a solution of 50% strength of boron trifiuoride in diethyl ether (boron trifiuoride present in the form of its etherate) is heated to 80 C. and then allowed to cool. There are obtained 360 parts of a brown liquid in which tetrahydrobenzyl alcohol can no longer be detected; it consists substantially of 3- [A -tetrahydrobenzyl-hydroxyethyl 2 4-dioxospiro(5 5)-undecene-9.

(c) Epoxidation 320 parts of the above 3-[A -tetrahydrobenzyl-hydroxyethyl]2:4-dioxospiro-(525)-undecene-9 (crude product) are dissolved in 1000 parts by volume of benzene and 25 parts of sodium acetate are added. In the course of 20 minutes 462 parts of per-acetic acid of 39.5% strength are stirred in in portions, while maintaining the temperature at about 35 C. by intensive cooling. When the mixture has reacted for another 2 hours at 30 C. with stirring, the reaction is complete and the reaction mixture is cooled to room temperature. Titration reveals that the theoretical amount of pcracetic acid has been consumed.

The benzene solution is washed three times with 300 parts by volume of water and then with aqueous sodium hydroxide solution until it is neutral and washed twice more with 150 parts by volume of water. The benzene solution is dried over sodium sulfate, filtered and evaporated under reduced pressure. The last remnants of the solvent are expelled in a high vacuum at 100 C. There are obtained 317 parts of a pale-yellow liquid resin containing 5.3 epoxide equivalents per kg. and having a viscosity of about 25000 centipoises at 20 C.; it consists substantially of the diepoxide of the formula 1?. EXAMPLE 2 (a) Acetal of Acrolein and 1:1-Bis-[Hydr0xymetlzyl]-6- Methylcyclohexened A mixture of 56 parts of acrolein, 157 parts of 1:1-bis [hydroxymethyl]-6-rnethylcyclohexene-3 and 1 part of sulfuric acid of 50% strength is heated in a water bath at 40 C. until all has passed into solution. An exothermic reaction sets in so that after removal of the water bath the temperature rises to 50 C. 350 parts by volume of benzene are then added and the mixture is boiled for 40 minutes in a circulation distillation apparatus until 20 parts of water have passed over azeotropically. The solution is treated with 2 parts of anhydrous sodium acetate, filtered and evaporated. The benzene is distilled off under a vacuum of 0.5 mm. Hg at 81 C. and 163 parts of acetal [3-vinyl-7-methyl-2:4-dioxospiro(5:5)-undecene-9] pass over which corresponds to a yield of 83.6% of the theoretical. There remain 27 parts of an unidentified residue.

(12) Additive Reaction With M-Tetrahydrobenzyl Alcohol A mixture of 65 parts of the above acetal [3-vinyl-7- methyl-2:4-dioxospiro(5:5)-undecene-9], 38 parts of A tetrahydrobenzyl alcohol, 0.5 part of concentrated sulfuric acid and 0.5 part of a solution of 40% strength of boron trifluoride in diethyl ether (boron trifiuoride present as the etherate) is heated for 4 hours at C., left to itself for 15 hours, and then shaken with 2 parts of anhydrous sodium carbonate, to yield 101 parts of a liquid in which tetrahydrobenzyl alcohol can no longer be detected; it consists substantially of 3-[A -tetrahydrobenzyl-hydroxyethyl] -7-methyl-2 4-dioxospiro 5 :5 -undecene-9.

(c) Epoxidation A solution of 97 parts of the above 3-[A -tetrahydrobenzyl-hydroxyethyl] 7 methyl 2:4 dioxospiro(5 :5)- undecene-9 in 280 parts by volume of benzene is treated with 7 parts of anhydrous sodium acetate and in the course of 30 minutes 148 parts of peracetic acid of 39.5% strength are stirred in dropwise, while maintaining the temperature at 150-35 C. by external cooling. After 2 hours 91% of the theoretical amount of peracetic acid have been consumed. After 3 hours the reaction mixture is allowed to cool to room temperature, the aqueous bottom phase is separated and the supernatant phase washed three times with 100 parts by volume of water on each occasion, then neutralized by being shaken with 100 parts by volume of water containing 7 parts by volume of sodium hydroxide solution of 30% strength, then washed twice with 50 parts by volume of water on each occasion, dried over sodium sulfate, filtered and evaporated at 100 C. under a pressure of 0.15 mm. Hg. There are obtained 774 parts of a liquid, pale-yellow resin containing 4.5 epoxide equivalents per kg. and having a viscosity of 27,474 centipoises at 20 C. This resin consists substantially of the diepoxide of the formula /CH3 /0 CHg-CH CHz-O CHz-CH E CH-CIITCHTO-CIITCI'I /CI'I CIT-CH2 CHQO CIIrCH:

EXAMPLE 3 (a) Acetal of Cr tonic Aldehyde and 1 :1 -Bis-[Hydroxy- Metlzyl1-Cyclohexene-3 A mixture of 70 parts of crotonic aldehyde, 143 parts of 1:l-bis-[hydroxymethyl]-cyclohexene-3 and 0.8 part by volume of sulfuric acid of 50% strength is heated for 15 minutes at 50 C. until all has passed into solution and an exothermic reaction sets in. 350 parts by volume of benzene are added and the whole is boiled for 30 minutes in a circulation distillation apparatus until 18 parts of water have passed over azeotropically. The solu- 13 tion is treated with 2 parts of anhydrous sodium acetate, filtered and evaporated. The benzene is distilled oif at 92 C. under 0.5 mm. Hg and there are obtained 180 parts of acetal [3 propenyl 2:4 dioxospiro(5 :5 undecene-9] corresponding to 92% of the theoretical yield.

(b) Addition Reaction With M-Tetrahydrobenzyl Alcohol A mixture of 176 parts of the above acetal [3-propenyl- 2:4-dioxospiro(5:5)-undecene-9l, 105 parts of A -tetrahydrobenzyl alcohol and 0.8 part by volume of sulfuric acid of 50% strength is heated for 8 hours at 80 C., then left to itself for hours, and freed from unreacted tetrahydrobenzyl alcohol by evaporation under vacuum, 19 parts of the alcohol passing over at 40 C. under 0.15 mm. Hg. The residue amounts to 253 parts, corresponding to a yield of crude product of 92% consisting substantially of 3[A "-tetrahydrobenzoyloxy-(2)-propyll- 2:4-dioxospiro (5 5 -undecene-9.

(c) Epoxidalion A solution of 253 parts of the above 3-[A "-tetrahydrobenzoyloxy-(2')-propyll -2:4-dioxospiro( 5:5 undecene- 9 in 750 parts by volume of benzene is treated with 20 parts of anhydrous sodium acetate, and in the course of 45 minutes 340 parts of peracetic acid of 39.5% strength are stirred in dropwise, while maintaining the temperature at 30-35 C. by external cooling. After 2 hours the theoretical amount of peracetic acid has been consumed. The whole is allowed to cool to room temperature, the aqueous bottom phase is separated and the supernatant phase washed three times with 150 parts by volume of water on each occasion and then neutralized by being shaken with 100 parts by volume of water containing 7 parts by volume of sodium hydroxide solution of 30% strength, then washed twice with 100 parts by volume of water on each occasion, dried over sodium sulfate, filtered and evaporated at 100 C. under 15 mm. Hg in the course of 30 minutes. There are obtained 774 parts of a viscid yellow resin containing 5.1 epoxide equivalents per kg. and having a viscosity of 102,700 centipoises at 20 C.

This resin consists substantially of the diepoxide of the formula OHrCH CH2-O and can be cured with phthalic anhydride to form a pale,

infusibl resin.

EXAMPLE 5 A mixture of 22 parts of the cyclic acetal of 2 mols of acrolein and 1 mol of pentaerythrito-lrcferred to as 3:9-divinyl-spiro-bi-[meta-dioxane] or as 3:9-divinyl- 2:4:8:l0-tetraoxospiro(5:5)-undecaneand 22 parts of A -tetrahydrobenzyl alcohol is treated with 0.1 part of sulfuric acid of 60% strength and 0.2 part of a solution of 40% strength of boron trifluoride in diethyl ether. The mixture is heated for 12 hours at 80 C., after which time a viscid, yellowish brown product has formed in which tetrahydrobenzyl alcohol can no longer be detected and which consists substantially of the adduct 3:9-bis-[A tetrahydrobenzyl-hydroxyethyl] -spiro-bi- [meta-dioxane] A solution of parts of the above adduct in 140 parts by volume of benzene is treated with 4 parts of sodium acetate. In the course of 15 minutes 40 parts of peracetic acid of 42.8% strength are stirred in dropwise, while maintaining the temperature at 30 C. by cooling with ice. The mixture is then stirred for another 60 minutes at 30 C. and the aqueous bottom phase is separated. The benzene solution is Washed twice with parts by volume of water on each occasion, dried over sodium sulfate and evaporated, to yield a viscid resin containing 2.70 epoxide equivalents per kg. This resin consists substantially of the diepoxide of the formula o.oHoHi o-om cmo CHg-CH-O l OHCH.-.OOH2CHz-C I o CHCH2CHz-OCHz-C :n

CHrCI-Ig o-C CHz-O CH2C 0 and can be cured With phthalic anhydride to form a ()HrCH2 311 .9 CHTO I bright, infusible resin. on ornori'i-on o-om-o on 50 EXAMPLE 6 olt-og orig-o om GHQ-Chi A mixture of 91 parts of the cyclic triacetal of 3 mols gfdacrgleinlanld lhIllltOl oif sojrbitolt, 1f05 pagtskof A2422?- r enz a o o r 1 EXAMPLE 4 5 st iength of bor n trifl il hride iri t iietiiyl etii ei is lie ted fo r An acetal is prepared as described in the preceding examples from l07'parts of crotonic aldehyde and 229 parts of l: l-bis-[hydroxymethyl] -6-methylcyclohexene-3 in the presence of 1 mol of sulfuric acid of 50% strength and of benzene for the azeotropic distillation of the reaction water. When the reaction mixture is fractionated under vacuum, 270 parts of 3-propenyl-7-methyl-2r4- dioxospiro(5:5)undecene-9 pass over at 75-82 under 0.2 mm. Hg.

A mixture of 158 parts of this acetal, 75 parts of 6- methyl-A -tetrahydrobenzyl alcoholand 1.5 parts of a solution of 40% strength of boron trifluoride in diethyl ether is heated for 2 hours at 80 C. After 30 parts of forerunnings have been distilled off at 140 C. under 0.1 mm. Hg, there remain 230 parts of residue which consists substantially of the adduct of 3-.l6"-methyl-A "-tetrahydrobenzoy'loxy-(Z')-propyl-7 methyl 2:4 dioxospiro- (515)-undecene-9.

A mixture of 215 parts of this adduct and 600 parts by volume of benzene is treated with 16 parts of sodium 5 hours at C., allowed to cool, and 30 parts of unreacted tetrahydrobenzyl alcohol are then distilled out of the mixture at 45 C. under 0.15 mm. Hg. Thus, the residue consists of an adduct of exactly 2 mols of the alcohol and 1 mol of the triacetal. This adduct is epoxidized in the following manner:

A solution of 153 parts of the residue described above in 350 parts by volume of benzene is treated with 7 parts of sodium acetate. In the course of 35 minutes 134 parts of peracetic acid of 35.8% strength are stirred in drop- Wise, while maintaining the temperature at 3035 C. by cooling with ice. When the mixture is stirred for another 60 minutes at 30 C., the theoretical amount of peracetic acid has been consumed. The mixture is allowed to cool and the aqueous bottom phase is separated. The benzene solution is washed twice with parts by volume of water on each occasion and once with 100 parts by volume of aqueous 2 N-sodium hydroxide solution, then washed twice with 50 parts by volume of water, dried over sodium sulfate, filtered and evaporated under 0.5 mm. Hg pres- 15 sure, finally at 100 C. There are obtained 159 parts of a yellow, viscid resin containing 2.1 epoxide equivalents per kg. This resin can be cured with phthalic anhydride to form a bright, infusible resin.

EXAMPLE 7 A mixture of 23 parts of glycerol-mmonochlorohydrin and 36 parts of the acetal prepared as described in Example 1 from acrolein and 1:1-bis-[hydroxymethy1] cyclhexene-3 is treated with 0.5 part of a solution of 40% strength of boron trifiuoride in diethyl ether and heated for 80 minutes at 80 C.

The cycloolefinic double bond in the resulting adduct-- 3 [2 hydroxy-3'-chloropropoxyethyl]-2z4-dioxospiro- (5:5)-unclecene9-is epoxidized in the following manner:

The completely reacted reaction mixture described above 1 (about 59 parts) is treated with 150 parts of benzene and 5 parts of anhydrous sodium acetate. While stirring and cooling with ice 36 parts of peracetic acid of 42.8% strength are added dropwise within minutes at 30 C., and the mixture is then stirred on for minutes at 30 C., after which time the theoretical amount of peractic acid has been consumed and the mixture is then worked up as described in the preceding examples, to yield 52 parts of monoepoxidized chlorohydrin.

The resulting monoepoxide is converted into a diepoxide in the following manner:

The 52 parts of the above epoxidized chlorohydrin 3 [2-hydroxy-3'-chloropropoxyethyl]-9:10-epoxy-2z4- dioxospiro(5:5)undecanenre treated with 27 parts of aqueous sodium hydroxide solution of 28% strength and the whole is heated for one hour at 50 C. 100 parts of benzene are then added and the precipitated solid sodium chloride is filtered off. The benzene layer is separated, washed until neutral and finally evaporated in a high vacuum, to yield 42 parts of a pale-yellow, liquid epoxy resin consisting substantially of the diepoxide compound of the formula With the aid of phthalic anhydride it can be cured to form a practically colorless, infusible resin.

EXAMPLE 8 A mixture of 45 parts of glycerol-a-monochlorohydrin and 43 parts of the cyclic acetal of 1 mol of pentaerythritol and 2 mols of acrolein-3:9-divinyl-spiro-bi-[meta-dioxane]is treated with 0.5 part of a solution of 45% strength of boron tritluoride. For 15 minutes a weakly exotherrnic reaction can be observed, after the completion of which free glycerol*m-monochlorohydrin can no longer be detected in the reaction mixture. The whole is then allowed to cool, treated with 63 parts of aqueous sodium hydroxide solution of 28% strength and heated with vigorous stirring for one hour at 45 C. The solid sodium chloride is then filtered oil, the benzene solution is separated and evaporated, to yield as residue parts of a viscid pale-yellow resin containing 1.8 epoxide equivalents per kg. which consists substantially of the diepoxide of the formula and can be cured with phthalic anhydride to form an infusible resin which is only slightly tinted.

EXAMPLE 9 Phthalie anhydride as curing agent is dissolved in Impact bend- Bending Test mg strength, strength,

0111. kgjsqu. cm. kgJsqu. mm.

A second portion of each of the above mixtures is cast in a layer about 0.1 mm. and 1 mm. thick on plates of glass and then cured for 24 hours at 140 C. The films cured in this manner adhere excellently to the sup port and are resistant towards 5 N-sulfric acid, 5 N-sodium hydroxide solution, water, acetone and chlorobenzene after exposure thereto for one hour at room temperature.

EXAMPLE 10 100 parts of the polyepoxy resin prepared as described in Example 1 are mixed at room temperature with 11.9 parts of 2:4-dihydroxy-3-hydroxymethylpentane, and in this mixture 51 parts of phthalic anhydride are dissolved at -125. C. as curing agent. When, as described in Example 9, this mixture (about 90 grams) is cast in aluminum moulds it gels at 120 C. within about one hour, that is to say that the originally liquid mixture has soliditied to form a gel. After having been cured for 24 hours at 140 C. the casting displays an impact bending strength of 12.7 cm. kg./sq. cm. and a bending strength of 16.0 kg./squ. mm.

EXAMPLE 11 51 parts of phthalic anhydride (0.65 equivalent of anhydride groups per equivalent of epoxide groups) are dissolved at 120 to C. in 100 parts of a polyepoxy resin prepared as described in Example 1. At 120 C. the mixture has a viscosity below 10 centipoises and after 2 /2 hours of 1500 centipoises. The mixture is east in aluminum moulds as described in Example 9. Curing is carried out in two stages, first for 24 hours at C. and then for 24 hours at 200 C. The resulting casting 50 has an outstandingly high thermal stability of over 235 (measured according to Martens DIN).

EXAMPLE 12 594 parts of a sodium alcoholate prepared by dissolving 0.41 part of sodium metal at about 120 C. in 100 parts of 2:4-dihydroxy-3-hydroxymethylpentane are dissolved at room temperature in 100 parts of the epoxy resin prepared as described in Example 1. 1.0 equivalent of phthalic anhydride per equivalent of epoxide groups is fused in as curing agent at 120125 C. A first portion of the mixture is cast in aluminum moulds as described in Example 9 and cured for 24 hours at 140 C. The resulting casting has the following properties:

Impact bending strength 13.6 cm. kg./squ. cm. 65 Bending strength 14.8 kg./squ. mm.

Thermal stability according to Martens DIN 166.

Another portion of the above mixture is used for cementing tests in which degreased and ground strips of aluminum (170 x 25 x 1.5 mm.; overlap 10 mm.) 7 marketed under the trade name Anticorodal B are 17 cemented together. The curing of the cemented joint is carried out for 24 hours at 140 C.

At dilferent test temperatures the following tensile shear stresses are obtained:

arated. The benzene layer is washed three times with 400 Tensiletshear parts by volume of water on each occasion, 120 parts of Test temperutureiu 0. Strength, sodium hydroxide solution of 30% strength being added f P- I to the third washing water in order to neutralize any remaining acetic acid. The layer is then washed once more $0111 tempemwm 32 with 200 parts by volume of water, the solvent is distilled 150 0.88 off under a partial water-jet vacuum and the residue is 158 8:32 freed from last remnants of volatile constituents by beingheated at 100 C. under 0.1 mm. Hg. In this manner there are obtained 563 parts of a pale-yellow oil which As is shown by this table the cemented joints display contains 4.18 epoxide equivalents per kg. (95% of the excellent tensile shear strengths, above all at the extheoretical content) and consists substantially of the com tremely high test temperature of ISO-190 C. pound of the formula CH2 CHZO OCH; CH2

CH 0 OHOH2CH2OOH2CH2OCH2CH2CH c CH 0 CH 0 f 2 0o 2 0 CH '/CH2 CH; CH on, om EXAMPLE 13 When this oil is hardened with phthalic anhydride (0.7 100 parts of the polyepoxy resin prepared as deequivalent of anhydfide groups P q f 0f PQ scribed in Example 3 are fused together with 45.6 parts o ps) r 24 hours at 9 a g y tlnted, fiexlble, of phthalic anhydride as curing agent at 120-125 0.6 Sohd, lnfllslble Teslnis Obtainede uivalent of anhydride groups being used vfor every eguivalent of epoxidegroups of the resin. The mixtures EXAMPLE are cured in aluminum mould X X 9 198 parts of the acetal described in Example 1(a) of for 24 at 150 The castmg Cured t'hls acrolein and l: l-bis-[hydroxymethyl]-cyclohexene-3 are Her has an U i bending Strength of kg/squ' heated with 38 parts of trimethylene glycol to- 80 C. and and a bendmg Strength of kg/squ' 35 0.5 part of concentrated sulfuric acid is added, whereupon EXAMPLE 14 a slight increase in temperature is observed. As de- 25 parts of a boron trifiuoride/monoethylamine scribed in Example 15, the reaction mixture is then main- Plex are dissolved in 50 parts of the polyepoxy resin tamed for hours at 85-90" C., and then treated with 1 pared as described in Example The mixture is cast part of sod1um carbonate, whereupon 18 parts of excess in an iron mould and cured for 16 hours at Q The 44 v acetal are caused to pass over under a pressure of 0.2 mm. resulting casting has a thermal stability of 138 (meas- E 2101mm of trimfithylene Y ured according to Mal-tens DIN). droxosprro-S:5) undecene-9-yl-(3)-ethyl]-ether in the form of a viscous, yellow oil which is epoxidized by tak- EXAMPLE 15 ing it up with 600 parts by volume of benzene, adding 1 A mixture of 86 parts of ethylene glycol and 550 parts. part of anhydrous sodium acetate and dropping in 198- Of the ac l Ob according to Example from parts of 40.7% peracetic acid in the course of 30 minutes 1:l-lbis-[hydroxym thyll-CYC 0 6 a d aC at 35 C. After having stirred the mixture for a further vinyl-2:4-di0xospiro-5:5-undecene-9) is heated to 80 C., 2 'hours at 35 C., 97% of the theoretical amount of and 1 part of concentrated sulfuric acid is stirred in, oxidizing agent have been consumed. Further working whereupon the temperature rises eh y- The reaction up follows the auerii of Example 15, to yield finally 198 mix e i e heated for Z'hOUIS at u at fi parts of a pale-yellow oil containing 3.82 epoxide equivawith sli ht cooling and after the evolution of heat has lents per kg. (90% of the theoretical content) which con-- subsided by ea g 011 an bath. The cid is then sists substantially of the diepoxide of the formula 0H2 CH2O I 00112 CH C r t o c o t t a I :I H2Q (QH2)2OCH2CH3CI\I O CL\I\ O\' CHzO .OC 2] i0 Churn. CH2 Y C i neutralized with 2 parts of sodium Carbona e, a d 41 When thisproduct is cured with phthalic anhydride as de-; parts f eXCcSS 366131, P g Over at C- llflder .3l scribed in Example 15, a flexible, solid, infusible resinis mm. Hg, aredistilled outof the reaction mixture. The obtained. ethylene glycol has reacted completely. The resulting distillation residue consists of 578 parts of crude ethylene EXAMPLE 17 glycol-bis-[2-(2:4-dioxospiro Sz5') undecene-9'-yl- A mixture of 46parts of 1:4-butanediol and 200 parts (3)-ethyl]-ether in the form of apale-brown oil. of the acetal described in Example 1(a) of acrolein and The 578 parts of the adduct described above are taken lzl-bis-[hydroxymethyl]-cyclohexene-3 is heated to 80 up with 1700 parts by volume of benzene, 30 parts of C., and 0.5 part of concentrated sulfuric acid is added, anhydrous sodium acetate are added and the mixture whereupon the temperature rises slightly. While stirring is heated to 35 C. In the course of 30 minutes 555' themixture thoroughly the temperature is maintained for parts of peracetic acid of 41.3% strength are then addeddropwise while maintaining a temperature of 35 C. which is kept up for another 2 hours after the whole of the oxidizing agent has been added dropwise' At first the reaction mixture must be slightly cooled for about mml-Hg,

18 1 hours and after that this temperature is maintained by heating. After the indicated time the theoretical amount of oxidizing agent has been consumed.

The whole is then cooled and the aqueous phase is sep- 2 hours at -90 C., at first with slight cooling and after the evolution of heat has subsided by heating. 1 part of anhydrous sodium carbonate is then added and 20 parts of excess acetal are distilled off at 50 C. under 0.3 which corresponds exactly to the initially added 19 20 excess. There remain as distillation residue 223 parts of a polyethylene glycol of average molecular weight 300 butanediol bis [2-(2':4'-dioxospiro-5:5')-undecene-9- is heated to 80 C. After addition of 1 part of sulfuric yl-(3)-ethyl]-ether in the form of a dark, viscous oil. acid and 0.5 part of boron trifiuoride etherate (48% The latter oil is epoxidized in the following manner: strength) no rise in temperature is observed. The tem- The crude Pmdllct is taken P in 600 Parts by Volume of 5 perature is then maintained by heating for 3 /2 hours at benzene, parts of anhydrous sodium acetate are added 5.90 and the mixture is than neutralized d 23 and m course of mmutes at 196 parts of excess acetal are distilled otf, to leave 492 parts peracenc acid of 40.8% strength are added dropwise. of a viscous, brown liquid.

The oxidation is carried on for another 3 hours and the Said liquid is taken up with 1470 parts by volume of desired.temperamre of 35 o is maintained first 2 10 benzene, treated with 16 parts of anhydrous sodium ace 1?, coolmg and later on heatmg' Aft'ter -md1cated tate and epoxidized with 310 parts of peracetic acid of time 98.5% of the theoretical amount of OXldlZlIlg agent 8% Stren th for 3 hours at C whereby 100% of 222 13;}g ffi fi ggi f'fi g gff fif if 1:12:23 a the theoretical amount of oxidizing agent are consumed. last traces of volatile constituents in a high vacuum there 15 After Washing, flelltfalllatlon and concleutrzfiion 1therg are obtained in this manner 233 parts of a viscous, yellow are FF 418 of vlscous Pa q liquid which contains 3.95 epoxide equivalents per kg. Containing ePOXlde equlvalents P 8- Whlc a W (94.5% of the theoretical content) and consists substanhaving been hardened for 24 hours at with tially of the diepoxide of the formula pht halic anhydride (0.65 equivalent of anhydride groups CH1 c1120 OCH: CH2 on 0 onomomowmnoomcmcfl o \CH o L l oHio 0o 2| Jjo H H: CH7

C 2 cz When this product is cured for 24 hours at 140 C. with peer equivalent of epoxide groups), forms a flexible, inphthalic anhydride (0.7 equivalent of anhydride groups fusible resin.

per equivalent of epoxide groups), a pale-yellow, flexible, 30 EXAMPLE 21 Sohd mfuslble resm 1S Obtamed A mixture of 279 parts of the acetal of acrolein and EXAMPLE 18 1:1-bis-[hydroxymethyl]-cyclohexene-3 and 319 parts of polypropylene glycol (average molecular weight 425) is heated to 85 C. and treated with 1 part of concentrated sulfuric acid, whereby no heating up occurs. 0.5 part of boron trifiuoride etherate of 40% strength is then added, whereupon the temperature rises very slightly and is maintained for 6 hours at 8590 C. After neu- 40 tr-alization with 3 parts of sodium carbonate and distilling off the excess acetal, there remain 586 parts of a viscous, dark liquid.

The latter liquid is taken up in 1500 parts by volume of benzene, treated with 14 parts of anhydrous sodium carbonate and epoxidized with 284 parts of peracetic acid of 44.2% strength. The theoretical amount of oxidizing agent 'is consumed. After working up as described in Example 15 there are obtained 585 parts of a very VIS- cous, yellow liquid containing 2.17 epoxide equivalents per kg. (89% of the theoretical content).

A mixture of 87 parts of pentanediol-l:5 and 298 parts of the acetal described in Example 1(a) of acrolein and 35 l:l-bis-[hydroxymethyl-cyclohexene-3 is heated to 80 C., 1 part of concentrated sulfuric acid is added, whereupon the temperature rises slightly. The temperature is maintained for 3 hours at 8590 C. and the reaction mixture is then neutralized with 1 part of anhydrous sodium carbonate. 20 parts of excess acetal are then distilled off in a high vacuum to yield as residue 349 parts of pentanediol-bis-[2-(2':4'-dioxospiro-5:5) -undecene- 9'-yl-(3)-et-hyl]-ether in the form of a dark, viscous liquid.

These 349 parts are taken up in 1050 parts by volume of benzene, treated with 16 parts of anhydrous sodium acetate and epoxidized, as described in Example 15, with 309 parts of peracetic acid of 40.7% strength. Working up is performed as described in Example 15. There are finally obtained 362 parts of a viscous, yellow liquid containing 3.84 epoxide equivalents per kg. (95.3% of the theoretical content).

equivalent of anhydride groups per equivalent of epoxide groups) furnishes a very flexible and plastic casting.

EXAMPLE 19 5F EXAMPLE 22 0 A mixture of 198 parts of the acetal described in Ex- 369 parts of the acetal of acrolein and 1:1-b1s-[hyample 1(a) of acrolein and 1:l-bis-[hydroxymethyl]-cydroxymethyl]-cyclohexene-3 and 106 parts of transclohexene-3 and 100 parts of polyethyleneglycol (averquinitol are heated to 80 C., the quinitol passing only age molecular weight 200) is heated to 80 C., 1 part partially into solution. Upon addition of 1 part of sulof concentrated sulfuric acid is added and the tempera furic acid a slight rise in temperature is observed and ture is maintained for 2 hours at 85-90 C.; after neuthe remainder of the quinitol dissolves slowly. The temtralization with 1 part of anhydrous sodium carbonate perature is maintained for 3 hours at 90-95 C. and the 17 parts of excess acetal are distilled off under 0.2 mm. reaction mixture is then cooled whereupon it crystallizes. Hg pressure, to yield as residue 270 parts of a viscous, 458 parts of the resulting crude mixture are dissolved brown liquid. in 1200 parts by volume of benzene and 20 parts of an- Said liquid is taken up in 800 parts by volume of ben hydrous sodium carbonate are added. The mixture is zene, treated with 10 parts of anhydrous sodium acetate then heated at 35 C. and in the course of 30 minutes and epoxidized with 198 parts of peracetic acid of 40.8% 390 .parts of peracetic acid of 43.4% strength are added Strength After Washing Concentration there are dropwise, whereupon the mixture is stirred on for 2 hours Curing of this product with phthalic anhydride (one,

obtained 273 parts of a viscous, yellow liquid containing at the same temperature, cooled, the aqueous layer is epoXide equivalents P g- (959% Of e 6 separated and the benzene layer is worked up as described Cal Conten in Example 15. There are obtained 427 parts of a slightly EXAMPLE 20 I tinted compound which crystallizes on cooling and con- A mixture of 298 parts of the acetal of acrolein and tains 3.72 epoxide equivalents per kg. (94.2% of the 1:l-bis-[hydroxymethyl]-cyclohexene-3 and 225 parts of theoretical content).

EXAMPLE 23 A mixture of 217 parts of the acetal prepared as described in Example 3(a), consisting of lzl-bis-[hydroxymethylJ-cyclohexene-3 and crotonic aldehyde, and 31 parts of ethylene glycol is heated to 80 C. and then treated with 2 parts of sulfuric acid, whereupon no heating up occurs. The mixture is then heated on an oil bath to 105 C., whereupon a slightly exothermic reaction sets in. The temperature is maintained for a further 2 hours at 105 C., whereupon 2 parts of sodium carbonate are added and 15 parts of excess acetal are distilled off, to leave 227 parts of a viscous, dark liquid.

The latter liquid is taken up with 660 parts by volume of benzene, treated with 18 parts of anhydrous sodium carbonate and epoxidized with 216 parts of peracetic acid of 39.5% strength as described in Example 15. Working up as described in Example 15 yields 211 parts of a very viscous, orange-colored liquid containing 3.75 epoxide equivalents per kg. (90.5% of the theoretical content).

EXAMPLE 24 A mixture of 276 parts of the acetal of acrolein and 1:l-bis-[hydroxymethyl]-cyclohexene-3 and 225 parts of dihydrodicyclopentadienol-S is heated to 85 C. and 0.5 part of sulfuric acid of 98% strength is added, whereupon the temperature rises spontaneously. The temperature is maintained for 24 hours at 90 C., at first by cooling and then by heating. The resulting adduct is then epoxidized in the following manner:

The adduct is treated with 1350 parts of benzene and 35 parts of sodium acetate and then heated to 35 C. In the course of 30 minutes 576 parts of peracetic acid of 43.6% strength are then added. The temperature is maintained for another 2% hours at 35 C., at first by cooling and then by heating. The product is then washed, neutralized and concentrated as described in Example 1(c), to yield finally 505 parts of a viscous, yellow liquid containing 5.15 epoxide equivalents per kg. (93.3% of the theoretical content) which consists substantially of the compound of the formula The latter product is cured wtih phthalic anhydride (0.7 equivalent of anhydride groups per equivalent of epoxide groups) for 24 hours at 140 C, to form a bright, yellow, infusible resin having a thermal stability of 180 (Martens, DIN) and possessing good mechanical properties.

EXAMPLE 25 A mixture of 268 parts of octadecenyl alcohol and 186 parts of the acetal described in Example 1(a) of acrolein and 1:l-bis-[hydroxymethyl]-cyclohexene-3 is heated to 85 C. and 0.5 part of sulfuric acid of 98% strength is added, whereupon slight heating up occurs. The temperature is maintained for 3 hours at 90 C. 1 part of sodium carbonate is then added and the mixture is heated to 110 C. under 0.2 mm. Hg which causes no distillation. The adduct obtained in this manner is a viscous, yellow liquid.

The latter product is epoxidized in the following manner:

1150 parts of benzene and 20 parts of sodium acetate are added and the mixture is heated to 35 C., whereupon within 20 minutes 384 parts of peracetic acid of 43.5% strength are added; the temperature is then maintained for 2% hours at 35 C., after which time the theoretical amount of oxidizing agent has reacted. The product is washed, neutralized and concentrated at a final temperature of 115 C. under 0.1 mm. Hg. There are obtained 458 parts of a viscous, yellow liquid contain ing 3.64 epoxide equivalents per kg. When thisproduct is cured for 24 hours at 140 with phthalic anhydride (0.7 equivalent anhydride groups per equivalent of epoxide groups) it forms a bright, yellow, flexible and infusible resin. 7

EXAMPLE 26 A mixture of 22.5 parts of water and 450 parts of the acetal described in Example 1(a) of acrolein and 1 :1-bis- [hydroxymethyl]-cyclohexene-3 is heated to 80 C. and then treated with 3.5 parts of para-toluenesulfonic acid, whereupon the temperature rises slightly and the reaction mixture begins to boil under reflux. The boiling point rises gradually and reaches after 5 hours 90 C. at a bath temperature of 102 C. At this point the bulk of the water has reacted. The acid is then neutralized with 5 parts of sodium carbonate, and 3 parts of water and 4 parts of unreacted acetal are distilled 01f, to leave 461 parts of bis-[2-(2:4-dioxospiro 5'z5) undecene-9-yl- ('3') -ethyl] -ether in the form of a dark oil. Determination of the content of double bonds by hydrogenation reveals 98.5% of the theoretical content.

566 parts of the resulting unsaturated ether acetal are taken up in 1530 parts of benzene, 35 parts of sodium acetate are added and the mixture is heated to 35 C. and then treated within 30 minutes with 580 parts of peracetic acid of 43.2% strength. The temperature is maintained for 2% hours at 35 C., at first by cooling and then by heating. The aqueous layer is separated and the benzene layer is washed, neutralized and concentrated as described in Example 1, to yield 420 parts of a highly viscous, yellow product containing 4.40 epoxide equivalents per kg.

and consisting substantially of the diepoxide of the.

formula CH2 (311 .0 0.0 g cm C \C/ OHCHaCHzOCHzCHzCE \O/ \CH o l 011.6 oofzl Po OH I OH, CH: g Ca cz After having been cured with phthalic anhydride (0.6

EXAMPLE 2? A mixture of 90 parts of 3-vinyl-2:4-dioxospiro-(5:5)- undecene-9 (acetal from A -cyclohexene-1zl-dirnethanol and acrolein), 90 parts of the Diels-Alder adduct of 1:4-. butanediol with hexachlorocyclopentadiene and 0.5 part by volume of concentrated sulfuric acid is heated for.4 hours at C. The solid Diels-Alder adduct slowly dissolves. When the reaction is complete, a highly viscous liquid is obtained which does not contain any starting ma-. terial. I

The so-obtained product is dissolved in 430 parts of benzene and, after the addition of 5 parts of anhydrous sodium acetate, epoxidized with 87 parts of peracetic acid of 43.6% strength at 35 C. as described in the preceding examples. The reaction requires for completion 3 hours at 35 C. The oxidated reaction product is worked up in an analogous manner to that described in the preceding examples. There are obtained 152 parts of a product crystallized in the cold which contains 2.1

epoxide equivalents per kg. and which consists chiefly of the diepoxide of the formula pale yellow mobile liquid containing 5.5 epoxide equivalents per kg. (86.5% of the theoretical yield) which consists chiefly of the diepoxide of the formula The product can be cured with an acid anhydride, such as phthalic anhydride, to form sparingly combustible or incombustible castings.

What is claimed is: l. A diepoxy compound of the formula 1 EXAMPLE 28 A mixture of 630 parts of 3-vinyl-2:4-dioxo-spiro-(5 :5

undecene-9, 434 parts of ethylene glycol and 4 parts of 1 z' paratoluene sulfonic acid is heated for 90 minutes at 90 30 R G C. The mixture is then cooled, the acid is neutralized g 2 2- C C with 5 parts of anhydrous Na CO and the reaction g Product subjected to fractional distillation. There are ob- \l l X1 1 l l tained at 5294 C. under 0.15 mm. of pressure of mer- R4 R! Br- 0 cury 260 parts of unreacted ethylene glycol, at 125-130 35 4 C. under 0.15 mm. of pressure of mercury 500 parts of \R R/ R unsaturated alcohol 3-hydroxyethoxyethyl 2:4 dioxospiro-(5:5)undecene-9 and as residue 230 parts of the addition product of 2 mols of acetal and 1 mol of ethylene glycol.

The resulting unsaturated alcohol is converted into the corresponding chlorhydrin as follows:

363 parts of the above described 3-hydroxyethoxyethyl- 2:4-diox0spiro-(5:5)-undecene-9 and 1 part of borontrifluorideetherate of 40% strength are heated at 80 C. 153 parts of epichlorhydrin are added dropwise in the course of minutes to the well stirred mixture, care being taken that a temperature of 80-85 C. is maintained, if necessary by cooling. Stirring is then continued g at the same temperature for 30 minutes. At the end of so CH CH-CHr-O-CHz-CH2-CH e on this time no unreacted starting material is detectable.

515 parts of a viscous yellow liquid are obtained. 6

The resulting chlorhydrin is epoxidized as follows. The CH E resulting 515 parts of chlorhydrin are dissolved in 1390 CH1 on,

parts of benzene, parts of anhydrous sodium acetate are added and 219 parts of peracetic acid of 43.2% The dlepoxlde compound of the formula strength are added dropwise in the course of minutes CH; O-CH: CH: at C. with cooling. Stirring is continued for 3 hours. Q The aqueous layer is then separated, the organic phase washed and neutralized and the solvent evaporated in an analogous manner to that described in the preceding CH CH-CH; CH2 0 examples. There are obtained 486 parts of a yellow CH2 viscous liquid containing 2.63 epoxide equivalents per (92% of the theoretical yield). 4. The drepoxrde compound of the formula The resulting reaction product is then dehydrohalo- 55 genated as follows:

479 parts of the resulting epoxidized product are vigor- CH CHFO CH ously stirred with 365 parts of sodium hydroxide solution a O-G -11 L l/O of 30% strength for 1 /2 hours at 50-55 C. 800 parts 011 H2 H of benzene are then added, the aqueous layer is separated Cr cfi,

and the benzene distilled otf from the'organic layer under reduced pressure the vacuum being increased to 0.1 mm. No references cited. 

1. A DIEPOXY COMPOUND OF THE FORMULA 